Photoactive polymer materials

ABSTRACT

The present invention relates to novel photoactive polymer materials their use as orienting layer for liquid crystals, which are used for the production of non-structured and structured optical elements or electro-optical elements and multi-layer systems.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage of International Application No.PCT/EP2011/073540, filed on Dec, 21, 2011, which claims priority fromEuropean Patent Application No. 10196725.5, filed on Dec. 23, 2010, thecontents of all of which are incorporated herein by reference in theirentirety.

The present invention is concerned with novel photoactive polymermaterials their use as orienting layer for liquid crystals, which areused for the production of non-structured and structured opticalelements or electro-optical elements and multi-layer systems.

Optical elements or electro-optical elements are used for example assecurity devices, liquid crystal device (LCD), optical films, such asretarders like 3 D retarder. There are photoreactive compounds,described in U.S. Pat. No. 6,107,427 which can be used as orientationlayer for liquid crystals.

However, there is an increasing demand for advanced orienting materialsgiving access to efficient manufacturing processes, such as roll-toroll-processes, and which materials can be coated on differentsubstrates, and providing good orientation for liquid crystals.

The object of the invention is therefore to provide novel photoreactivepolymers which provide good orientation and give access to efficientmanufacturing process.

The present invention relates to polymer material which comprisesrepeating units of formula (I):

-   -   wherein

-   M¹ is a monomer unit selected from the group consisting of acrylate,    methacrylate, 2-chloroacrylate, 2-phenylacrylate, acrylamide,    methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, N-lower    alkyl substituted acrylamide, N-lower alkyl substituted    methacrylamide, N-lower alkyl substituted 2-chloroacrylamide,    N-lower alkyl substituted 2-phenylacrylamide, vinyl ether, vinyl    ester, styrene, diamine, amide, imide, siloxane, amic ester, amic    acid; preferred is a monomer unit selected from the group consisting    of acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate,    acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide,    N-lower alkyl substituted acrylamide, N-lower alkyl substituted    methacrylamide, N-lower alkyl substituted 2-chloroacrylamide,    N-lower alkyl substituted 2-phenylacrylamide, vinyl ether, vinyl    ester, styrene, siloxane, diamine, amide, amic ester, amic acid;    more preferred is a monomer unit selected from the group consisting    of acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, vinyl    ether, vinyl ester, styrene, siloxane; most preferred is acrylate or    methacrylate,

-   ring A is unsubstituted phenylene, phenylene which is substituted    with fluorine, chlorine, cyano, alkyl or alkoxy, pyridine-2,5-diyl,    pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, cyclohexane-1,4-diyl,    piperidine-1,4-diyl, or piperazine-1,4-diyl; preferred is phenylene,

-   ring B is unsubstituted phenylene, phenylene which is substituted    with fluorine, chlorine, cyano, alkyl or alkoxy, pyridine-2,5-diyl,    pyrimidine-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene,    1,3-dioxane-2,5-diyl, or cyclohexane-1,4-diyl; preferred is    phenylene,

-   Y¹, Y² each independently is a single covalent bond, —(CH₂)_(t)—,    —O—, —CO—, —CO—O—, —O—OC—, —NR⁴—, —CO—NR⁴—, —R⁴N—CO—, —(CH₂)_(u)—O—,    —O—(CH₂)_(u)—, —CF₂O—, —OCF₂—, —(CH₂)_(u)—NR⁴—, or —NR⁴—(CH₂)_(u)—,    in which

-   R⁴ is hydrogen or lower alkyl;

-   t is a whole number from 1 to 4;

-   u is a whole number from 1 to 3;

-   m, n each independently is 0 or 1;

-   ring C is unsubstituted phenylene, phenylene which is substituted    with fluorine, chlorine, cyano, alkyl or alkoxy,    pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene,    2,5-furanylene, 1,4-naphthlene, or 2,6-naphthylene;

-   S¹ is a spacer unit, wherein if m and n are 0 then the spacer unit    is S², and if at least one m or n is 1, preferably if m is 1 and n    is 0, then the spacer unit is S³; wherein S² is C₄-C₂₄alkylene and    S³ is C₉-C₂₄alkylene, preferably C₁₀-C₂₄alkylene, and wherein    -   alkylene is unsubstituted or substituted, straight-chain or        branched alkylene, in which one or more —CH₂— groups may be        replaced by at least one linking group, alicyclic or/and        aromatic group,

-   Z is —O— or —NR⁵—, in which R⁵ is hydrogen or lower alkyl, or a    second group of formula D, in which

-   D is hydrogen or an unsubstituted C₁-C₂₀ straight-chain alkylene    group, an unsubstituted C₁-C₂₀ branched-chain alkylene group, a    C₁-C₂₀ straight-chain alkylene group substituted with fluorine or    chlorine, a branched-chain C₁-C₂₀ alkylene group substituted with    fluorine or chlorine, an unsubstituted cycloalkyl residue with 3 to    8 ring atoms, or a cycloalkyl residue with 3 to 8 ring atoms    substituted with fluorine, chlorine, alkyl or alkoxy.

The term “linking group”, as used in the context of the presentinvention is preferably be selected from —O—, —CO, —CO—O—, —O—CO—,

—NR¹—, —NR¹—CO—, —CO—NR¹—, —NR¹—CO—O—, —O—CO—NR¹—, —NR¹—CO—NR¹—,—CH═CH—, —C≡C—, —O—CO—O—, and —Si(CH₃)₂—O—Si(CH₃)₂—, and wherein:

R¹ represents a hydrogen atom or C₁-C₆alkyl;

with the proviso that oxygen atoms of linking groups are not directlylinked to each other.

Preferably substituent of alkylene in S² or S³ is C₁-C₂₄-alkyl,preferably C₁-C₁₂-alkyl, more preferably C₁-C₈-alkyl; or hydroxy,fluorine, chlorine, cyano, ether, ester, amino, amido.

In the context of the present invention the term “polymer material”denotes oligomer, polymer, copolymer or homopolymer material.

In the context of the present invention the term “alkyl” is substitutedor unsubstituted, straight-chain or branched, saturated hydrocarbonresidues with a maximum of 20 carbon atoms, wherein one or more —CH₂— or—CH₃— groups may be unreplaced or replaced by at least one linkinggroup, or/and alicyclic or/and aromatic group.

The term “lower alkyl” taken alone or in combinations such as “loweralkoxy”, “hydroxy-lower alkyl”, “phenoxy-lower alkyl”, “phenyl-loweralkyl”, denotes, hereinbefore and hereinafter, straight-chain orbranched saturated hydrocarbon residues with 1 to 6, preferably with 1to 3, carbon atoms, such as methyl, ethyl, propyl, or i-propyl.

The term “alkyl” taken alone or in combinations such as “alkoxy”,denotes, hereinbefore and hereinafter, straight-chain or branchedsaturated hydrocarbon residues with a maximum of 20 carbon atoms.

The substituents of alkyl are or hydroxy, fluorine, chlorine, cyano,ether, ester, amino, amido, alicyclic or aromatic groups, wherein ineach one or more —CH₂— group may be replaced by at least one linkinggroup.

In the context of the present invention straight chain alkyl is forexample methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl,tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nondecyl, icosyl, henicosyl, docosyl, tricosyl orquatrocosyl, however not limited to it.

In the context of the present invention alicyclic group denotespreferably a substituted or unsubstituted non-aromatic carbocyclic orheterocyclic group and represents for example ring systems, with 3 to 30carbon atoms, as for example cyclopropane, cyclobutane, cyclopentane,cyclopentene, cyclohexane, cyclohexene, cyclohexadiene, decaline,adamantane, tetrahydrofuran, dioxane, dioxolane, pyrrolidine, piperidineor a steroidal skeleton such as cholesterol, wherein substituents arepreferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,more preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, and ostpreferred methyl, ethyl, propyl. Preferred alicyclic group iscyclopentane, cyclopentene, cyclohexane, cyclohexene, and more preferredare cyclopentane or cyclohexane.

In the context of the present invention aromatic group denotespreferably five, six, ten or 14 ring atoms, e.g. furan, benzene orphenylene, pyridine, pyrimidine, naphthalenen, which may form ringassemblies, such as biphenylene or triphenylen, which are uninterruptedor interrupted by at least a single heteroatom and/or at least a singlelinking group; or fused polycyclic systems, such as phenanthrene,tetraline. Preferably aromatic group are benzene, phenylene, biphenyleneor triphenylen. More preferred aromatic group are benzene, phenylene andbiphenylene. Most preferred is phenylene.

The term “phenylene which is unsubstituted or optionally substitutedwith fluorine, chlorine, cyano, alkyl or alkoxy” embraces in the scopeof the present invention 1,2-, 1,3- or 1,4-phenylene, especially however1,3- or 1,4-phenylene, which is unsubstituted or mono- ormultiply-substituted with fluorine, chlorine, cyano, alkyl or alkoxy,preferably with fluorine, methyl, ethyl, propyl, butyl, methoxy, ethoxy,propoxy, butoxy or cyano.

Especially preferred are 1,4-phenylene residues.

Examples of preferred phenylene residues are 1,3- or, 1,4-phenylene, 4-or 5-methyl-1,3-phenylene, 4- or 5-methoxy-1,3-phenylene, 4- or5-ethyl-1,3-phenylene, 4- or 5-ethoxy-1,3-phenylene, 2- or3-methyl-1,4-phenylene, 2- or 3-ethyl-1,4-phenylene, 2- or3-propyl-1,4-phenylene, 2- or 3-butyl-1,4-phenylene, 2- or3-methoxy-1,4-phenylene, 2- or 3-ethoxy-1,4-phenylene, 2- or3-propoxy-1,4-phenylene, 2- or 3-butoxy-1,4-phenylene, 2,3-, 2,6- or3,5-dimethyl-1,4-phenylene, 2,6- or 3,5-dimethoxy-1,4-phenylene, 2- or3-fluoro-1,4-phenylene, 2,3-, 2,6- or 3,5-difluoro-1,4-phenylene, 2- or3-chloro-1,4-phenylene, 2,3-, 2,6- or 3,5-dichloro-1,4-phenylene, 2- or3-cyano-1,4-phenylene, and the like.

In a more preferred embodiment of the invention S² or S³ is substitutedor unsubstituted, straight-chain or branched, —(CH₂)_(r)—, as well as—(CH₂)_(r)—O—, —(CH₂)_(r)—O—(CH₂)_(s)—, —(CH₂)_(r)—O—(CH₂)_(s)—O—,—(CH₂)_(r)—CO—, —(CH₂)_(r)—CO—O—, —(CH₂)_(r)—O—CO—, —(CH₂)_(r)—NR²—,—(CH₂)_(r)—CO—NR²—, —(CH₂)_(r)—NR²—CO—, —(CH₂)_(r)—NR²—CO—O— or—(CH₂)_(r)—NR²—CO—NR³—; preferably S² or S³ is optionally mono- ormultiply-substituted with C₁-C₂₄-alkyl, preferably C₁-C₁₂-alkyl, morepreferably C₁-C₈-alkyl, wherein alkyl has the above given meaning andpreferences; or S² or S³ is optionally mono- or multiply-substitutedwith hydroxy, fluorine, chlorine, cyano, ether, ester, amino, amido; andwherein one or more —CH₂— group may be replaced by a linking group,alicyclic or/and aromatic group;

wherein for S² the single suffix “r” is a whole number between 4 and 24,preferably between 5 and 12 and more preferably between 5 and 8,especially 6; and

for S³ the single suffix “r” is a whole number between 9 and 24,preferably between 9 and 12 and especially 9, 10, 11 or 12; and

wherein for S² the sum of the suffixes “r and s” is a whole numberbetween 1 and 24, preferably between 2 and 12 and more preferablybetween 5 and 8; and for S³ the sum of the suffixes “r and s” is a wholenumber between 7 and 24, preferably between 7 and 12 and especially 9,10, 11 or 12; and R² and R³ each independently signify hydrogen or loweralkyl.

In a most preferred embodiment of the invention S² or S³ isunsubstituted or unsubstituted, straight-chain or branched, —(CH₂)_(r)—,as well as —(CH₂)_(r)—O—, —(CH₂)_(r)—O—(CH₂)_(s)—,—(CH₂)_(r)—O—(CH₂)_(s)—O—, —(CH₂)_(r)—CO—, —(CH₂)_(r)—CO—O—,—(CH₂)_(r)—O—CO—, especially —(CH₂)_(r)—O—, —(CH₂)_(r)—O—(CH₂)_(s)—,—(CH₂)_(r)—O—(CH₂)_(s)—O—, —(CH₂)_(r)—CO—, —(CH₂)_(r)—CO—O—,—(CH₂)_(r)—O—CO—, more especially —(CH₂)_(r)—O— which is optionallymono- or multiply-substituted with C₁-C₂₄-alkyl, preferablyC₁-C₁₂-alkyl, more preferably C₁-C₈-alkyl; or hydroxy, fluorine,chlorine, cyano, ether, ester, amino, amido; and wherein one or more—CH₂— group may be replaced by a linking group, or an alicyclic oraromatic group; and wherein the single suffixes r and s and the sum ofthe suffixes s and r have the above given meanings and preferences; andR² and R³ each independently signify hydrogen or lower alkyl.

Examples of preferred “spacer units” S² are 1,6-hexylene, 1,7-heptylene,2-methyl-1,2-propylene, 1,3-butylene, ethyleneoxycarbonyl,ethyleneoyloxy, propyleneoxy, propyleneoxycarbonyl, propyleneoyloxy,butyleneoxy, butyleneoxycarbonyl, butyleneoyloxy, propyleneamino,butyleneamino, pentyleneamino, hexyleneamino, heptyleneamino,ethyleneaminocarbonyl, propyleneaminocarbonyl, butyleneaminocarbonyl,ethylenecarbonylamino, propylenecarbonylamino, butylenecarbonylamino,pentylenecarbonylamino, hexylenecarbonylamino, heptylenecarbonylamino,pentyleneaminocarbonyl, hexyleneaminocarbonyl, heptyleneaminocarbonyl,pentyleneoxy, pentyleneoxycarbonyl, pentyleneoyloxy, hexyleneoxy,hexyleneoxycarbonyl, hexyleneoyloxy, heptyleneoxy, heptyleneoxycarbonyl,heptyleneoyloxy, especially preferred is hexyleneoxy. Examples ofpreferred “spacer units” S³ are 1,9-nonylene, 1,10-decylene,1,11-undecylene, 1,12-dodecylene, nonylene-oxy, 1,11-undecyleneoxy,1,12-dodecyleneoxy, 1,11-undecyleneoxycarbonyl,1,12-dodecyleneoxycarbonyl, nonyleneoxycarbonyl, 1,11-undecyleneoyloxy,1,12-dodecyleneoyloxy, nonyleneoyloxy, 1,11-undecyleneamino,1,12-dodecyleneamino, nonyleneamino, 1,11-undecyleneaminocarbonyl,1,12-dodecyleneaminocarbonyl, nonyleneaminocarbonyl,1,11-undecylenecarbonylamino, 1,12-dodecylene carbonylamino,nonylenecarbonylamino, and the like.

Especially preferred “spacer units” S² are a straight-chain alkylenegrouping represented by —(CH₂)_(r)—, wherein r is 6, as well as—(CH₂)_(r)—O—, —(CH₂)_(r)—CO—O— and —(CH₂)_(r)—O—CO—.

Further, especially preferred “spacer units” S³ are a straight-chainalkylene grouping represented by —(CH₂)_(r)—, wherein r is 9, 10, 11,12, as well as —(CH₂)_(r)—O—, —(CH₂)_(r)—CO—O— and —(CH₂)_(r)—O—CO—.

Preferred is a polymer material which comprises repeating units offormula (I):

-   -   wherein

-   M¹ is a monomer unit selected from the group consisting of acrylate,    methacrylate,

-   ring A is unsubstituted phenylene or phenylene which is substituted    with alkyl or alkoxy,

-   ring B is unsubstituted phenylene or phenylene which is substituted    with fluorine, alkyl or alkoxy,

-   Y¹, Y² each independently is a single covalent bond, —CO—O—, —O—OC—,    in which

-   m, n each independently is 0 or 1;

-   ring C is unsubstituted phenylene or phenylene which is substituted    with alkyl or alkoxy;

-   S¹ is a spacer unit, wherein if m and n are 0 then the spacer unit    is S², and if at least one m or n is 1, preferably if m is 1 and n    is 0, then the spacer unit is S³; wherein S² is C₄-C₂₄alkylene,    preferably alkyleneoxy, or alkyleneoxycarbonyl, especially    propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy,    octyleneoxy, nonyleneoxy, deyleneoxy, or propylenoxycarbonyl,    butylenoxycarbonyl, pentylenoxycarbonyl, hexylenoxycarbonyl,    heptylenoxycarbonyl, octylenoxycarbonyl, nonylenoxycarbonyl,    deylenoxycarbonyl, and S³ is C₉-C₂₄alkylene, preferably    C₁₀-C₂₄alkylene, and wherein alkylene is unsubstituted or    substituted, straight-chain or branched alkylene, in which one or    more —CH₂— groups may be replaced by at least one linking group,    alicyclic or/and aromatic group,

-   Z is —O—,

-   D is hydrogen or an unsubstituted C₁-C₂₀ straight-chain alkyl group,    an unsubstituted C₁-C₂₀ branched-chain alkyl group, a C₁-C₂₀    straight-chain alkylene group substituted with fluorine or chlorine,    a branched-chain C₁-C₂₀ alkyl group substituted with fluorine or    chlorine, an unsubstituted cycloalkyl residue with 3 to 8 ring    atoms, or a cycloalkyl residue with 3 to 8 ring atoms substituted    with fluorine, chlorine, alkyl or alkoxy, preferably the C₁-C₂₀    alkyl group is methyl, ethyl, propyl.

The present invention relates in addition to a monomer compound offormula (I′):

-   -   wherein

-   M² is acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate,    acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide,    N-lower alkyl substituted acrylamide, N-lower alkyl substituted    methacrylamide, N-lower alkyl substituted 2-chloroacrylamide,    N-lower alkyl substituted 2-phenylacrylamide, vinyl ether, vinyl    ester, styrene, siloxane, diamine, amide, imide and siloxane, amic    ester; preferred is acrylate, methacrylate, 2-chloroacrylate,    2-phenylacrylate, acrylamide, methacrylamide, 2-chloroacrylamide,    2-phenylacrylamide, N-lower alkyl substituted acrylamide, N-lower    alkyl substituted methacrylamide, N-lower alkyl substituted    2-chloroacrylamide, N-lower alkyl substituted 2-phenylacrylamide,    vinyl ether, vinyl ester, styrene, siloxane; most preferred is    acrylate or methacrylate,    and S¹, A, B, C, D, Y¹, Y², n, m and z have the above given meanings    and preferences.

Preferred is a monomer compound of formula (I′): I

-   -   wherein

-   M² is a monomer unit selected from the group consisting of acrylate,    methacrylate,

-   ring A is unsubstituted phenylene or phenylene which is substituted    with alkyl or alkoxy,

-   ring B is unsubstituted phenylene or phenylene which is substituted    with fluorine, alkyl or alkoxy,

-   Y¹, Y² each independently is a single covalent bond, —CO—O—, —O—OC—,    in which

-   m, n each independently is 0 or 1;

-   ring C is unsubstituted phenylene or phenylene which is substituted    with alkyl or alkoxy;

-   S¹ is a spacer unit, wherein if m and n are 0 then the spacer unit    is S², and if at least one m or n is 1, preferably if m is 1 and n    is 0, then the spacer unit is S³; wherein S² is C₄-C₂₄alkylene,    preferably alkyleneoxy, or alkyleneoxycarbonyl, especially    propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy,    octyleneoxy, nonyleneoxy, deyleneoxy, or propylenoxycarbonyl,    butylenoxycarbonyl, pentylenoxycarbonyl, hexylenoxycarbonyl,    heptylenoxycarbonyl, octylenoxycarbonyl, nonylenoxycarbonyl,    deylenoxycarbonyl, and S³ is C₉-C₂₄alkylene, preferably    C₁₀-C₂₄alkylene, and wherein alkylene is unsubstituted or    substituted, straight-chain or branched alkylene, in which one or    more —CH₂— groups may be replaced by at least one linking group,    alicyclic or/and aromatic group,

-   Z is —O—,

-   D is hydrogen or an unsubstituted C₁-C₂₀ straight-chain alkyl group,    an unsubstituted C₁-C₂₀ branched-chain alkyl group, a C₁-C₂₀    straight-chain alkylene group substituted with fluorine or chlorine,    a branched-chain C₁-C₂₀ alkyl group substituted with fluorine or    chlorine, an unsubstituted cycloalkyl residue with 3 to 8 ring    atoms, or a cycloalkyl residue with 3 to 8 ring atoms substituted    with fluorine, chlorine, alkyl or alkoxy, preferably the C₁-C₂₀    alkyl group is methyl, ethyl, propyl.

The present invention also relates to a process for the preparation ofpolymer material which comprises repeating units of formula (I)comprising polymerising a monomer compound of formula (I′).

The monomers are accessible by method known in the art, the acrylate ormethacrylate monomers are for example accessible by reaction of thehydroxy cinnamate derivative with methacrylic acid, preferably in thepresence of DCC or by reaction with methacrylic anhydride in preferablythe presence of DMAP.

The present invention also relates to compositions (Ia), especially aformulation or/and a blend comprising a monomer of formula (I′), andoptionally a solvent, and optionally a further comonomer unit,preferably a comonomer unit of formula (I′), wherein at least one M¹, S¹A, Y¹, Y², n, B, m, C, z or D is different, and/or another comonomerwhich are usual in polymer chemistry.

Preferably, the composition comprises further solvents, such asespecially aprotic or protic polar solvents γ-butyrolactone,N,N-dimethylacetamide, N-methylpyrrolidone or N,N-dimethylformamide,methylethylketon (MEK), 1-methoxypropylacetat (MPA), alcohols,especially 1-methoxypropanol (MP). Preferred are aprotic polar solvents,especially γ-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidoneor N,N-dimethylformamide, methylethylketon (MEK), 1-methoxypropylacetat(MPA).

The polymer material in accordance with the invention can be synthesizedonly from repeating units of general formula I (homopolymers) or it cancontain further repeating units in addition to the repeating units ofgeneral formula I (copolymers). Preferred are copolymers with differentrepeating units. Homopolymers which contain structural units of formulaI are especially preferred. The polymers in accordance with theinvention have a molecular weight M_(W) between 1,000 and 5,000,000,preferably however between 5,000 and 2,000,000, especiallyadvantageously however between 10,000 and 1,000,000.

Comonomer units for the polymer materials in accordance with theinvention with C—C linkages in the main chain can be further structuresof formula (I) and/or however also other structures which are usual inpolymer chemistry, such as, for example, straight-chain or branchedalkyl esters of acrylic or methacrylic acid, allyl esters of acrylic ormethacrylic acid, alkyl vinyl ethers or esters, phenoxyalkyl acrylatesor phenoxyalkyl methacrylates, phenylalkyl acrylates or phenylalkylmethacrylates, hydroxyalkyl acrylates or hydroxyalkyl methacrylates withalkyl residues of 1 to 20, preferably 1 to 10, especially however with 1to 6, carbon atoms, acrylonitrile, methacrylonitrile, styrene,4-methylstyrene, and the like. Preferred comonomer units are structuresof formula I, alkyl esters of acrylic or methacrylic acid, hydroxyalkylacrylate, hydroxyalkyl methacrylate, acrylonitrile, methacrylonitrile orstyrene, but especially structures of formula I, alkyl esters of acrylicor methacrylic acid, hydroxyalkyl acrylate or hydroxyalkyl methacrylate.

Comonomer units for siloxanes are preferably further siloxane structuresof formula (I) and/or dimethyl siloxane groups.

The content of comonomer units in the polymers in accordance with theinvention, which do not correspond to a structure of formula (I), issmaller than or equal to 50%, preferably smaller than or equal to 30%,but especially smaller than or equal to 15%.

Under the term “copolymers” there are to be understood preferablystatistical copolymers such as, for example, copolymers from differentderivatives of formula (I) or from structures of formula I with acrylicacid, methacrylic acid or styrene derivatives. Homopolymers embracelinear and cyclic polymers such as, for example, cyclic polysiloxanes,but preferably linear polymers.

Repeating monomer units (M¹) are acrylates such as

acrylamides such as

vinyl ether and vinyl ester such as

styrene derivatives such as

siloxanes such as

wherein R¹ signifies hydrogen or lower alkyl;amide, imide, amic ester, amic acid or a mixture of imide and amic esteror/and acid such as the condensation product of a diamino comprisingalicyclic or aromatic (such as a diamino phenyl group) group with adianhydride (such as a tetracarboxylic dianhydride).

These condensation products lead to polyamic acid, polyimide, polyamicacid ester and mixtures thereof, which may be prepared in line withknown methods, such as those described in Plast. Eng. 36 (1996),(Polyimides, fundamentals and applications), Marcel Dekker, Inc. and inWO WO2007/071091, on page 64 second paragraph to page 68, line 29.

In a preferred embodiment, the present invention relates to a method,wherein a polyamic acid is obtained by reaction, preferablypolycondensation reaction, of at least one tetracarboxylic dianhydridewith at least one aromatic or alicyclic group having two amino groups.

A polyimide is obtained by the dehydration ring-closure of the abovepolyamic acid.

Preferred “monomer units” M¹ are acrylate, methacrylate,2-chloroacrylate, acrylamide, methacrylamide, 2-chloro-acrylamide,styrene derivatives and siloxanes. Acrylate, methacrylate, styrenederivatives and siloxanes are particularly preferred “monomer units” M¹.Quite especially preferred “monomer units” M¹ are acrylate, methacrylateand styrene derivatives.

Further, preferred polymer materials of the present invention consist ofcompounds of formula I in which

-   -   ring A signifies phenylene which is unsubstituted or optionally        substituted with fluorine, chlorine, cyano, alkyl or alkoxy,        pyridine-2,5-diyl, pyrimidine-2,5-diyl, cyclohexane-1,4-diyl;    -   ring B signifies phenylene which is unsubstituted or optionally        substituted with fluorine, chlorine, cyano, alkyl or alkoxy,        pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4- or 2,6-naphthylene,        cyclohexane-1,4-diyl;    -   Y¹, Y² each independently signify a single covalent bond,        —CH₂CH₂—, —O—, —CF₂O—, —OCF₂—, —CH₂—O—, —O—CH₂—, —CO—O— or        —O—OC—;        -   ring C signifies phenylene which is unsubstituted or            optionally substituted with fluorine, chlorine, cyano, alkyl            or alkoxy, or pyrimidine-2,5-diyl, pyridine-2,5-diyl,            2,5-furanylene, 1,4- or 2,6-naphthylene;    -   Z signifies —O— and    -   D signifies hydrogen or a straight-chain or branched alkylene        group with 1 to 20, especially with 1 to 12, carbon atoms or a        cycloalkyl residue with 5 or 6 ring atoms which is optionally        substituted with alkyl or alkoxy, especially with methyl or        methoxy, and    -   M¹ and S¹ m and n have the significance given above.    -   Especially preferred polymer materials consist of compounds of        formula I in which n=0 and    -   ring B signifies phenylene which is unsubstituted or optionally        substituted with fluorine, chlorine, cyano, alkyl or alkoxy,        pyridine-2,5-diyl, pyrimidine-2,5-diyl, cyclohexane-1,4-diyl;    -   Y² signifies a single covalent bond, —CO—O— or —O—OC—;    -   m signifies 0 or 1;    -   ring C signifies phenylene which is unsubstituted or optionally        substituted with fluorine, chlorine, cyano, alkyl or alkoxy, or        1,4- or 2,6-naphthylene;    -   Z signifies —O— and    -   D signifies hydrogen or a straight-chain or branched alkylene        group with 1 to 12 carbon atoms and M¹ and S¹ have the        significance given above.

The present invention provides polymer material which comprises withrepeating units of formula (Ia) are present,

-   -   wherein

-   M¹, M^(1′) each independently signify a repeating monomer unit from    the group; acrylate, methacrylate, 2-chloroacrylate,    2-phenylacrylate; optionally N-lower alkyl substituted acrylamide,    methacrylamide, 2-chloroacrylamide and 2-phenylacrylamide; vinyl    ether, vinyl ester, styrene derivative, siloxane, diamine, amide,    imide, siloxane, amic ester, amic acid; preferred each independently    signify a repeating monomer unit from the group; acrylate,    methacrylate, 2-chloroacrylate, 2-phenylacrylate; optionally N-lower    alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide and    2-phenylacrylamide; vinyl ether, vinyl ester, styrene derivative,    siloxane, siloxane; more preferred each independently signify a    repeating monomer unit from the group; acrylate, methacrylate,

-   S¹ is a spacer unit, wherein, if m and n are 0 then the spacer unit    is S² and if at least one m or n is 1, preferably if m is 1 and n is    0, then the spacer unit is S³;

-   S^(1′) is a spacer unit, wherein, if m′ and n′ are 0 then the spacer    unit is S^(2′) and if at least one m or n′ is 1, preferably if m′ is    1 and n′ is 0, then the spacer unit is S^(3′); wherein    -   S², S^(2′), S³ or S^(3′) are unsubstituted or unsubstituted,        straight-chain or branched, —(CH₂)_(r)—, as well as        —(CH₂)_(r)—O—, —(CH₂)_(r)—O—(CH₂)_(s)—,        —(CH₂)_(r)—O—(CH₂)_(s)—O—, —(CH₂)_(r)—CO—, —(CH₂)_(r)—CO—O—,        —(CH₂)_(r)—O—CO—, —(CH₂)_(r)—NR²—, —(CH₂)_(r)—CO—NR²—,        —(CH₂)_(r)—NR²—CO—, —(CH₂)_(r)—NR²—CO—O— or        —(CH₂)_(r)—NR²—CO—NR³—, which is optionally mono- or        multiply-substituted with C₁-C₂₄-alkyl, preferably C₁-C₁₂-alkyl,        more preferably C₁-C₈-alkyl; or hydroxy, fluorine, chlorine,        cyano, ether, ester, amino, amido; and wherein one or more —CH₂—        group may be replaced by a linking group, alicyclic or aromatic        group; and, in which r and s are each a whole number of 1 to 20,    -   with the proviso that 3≤r+s≤24, preferably 3≤r+s≤12 and more        preferably 3≤r+s≤8 for S²; and that 9≤r+s≤24, preferably        9≤r+s≤12 and more preferably 9≤r+s≤10 for S³; and R² and R³ each        independently signify hydrogen or lower alkyl; preferably S¹ and        S^(1′) have the above given preferences; and

-   rings A, A′ each independently signify phenylene which is    unsubstituted or optionally substituted with fluorine, chlorine,    cyano, alkyl or alkoxy, pyridine-2,5-diyl, pyrimidine-2,5-diyl,    1,3-dioxane-2,5-diyl, cyclohexane-1,4-diyl, piperidine-1,4-diyl,    piperazine-1,4-diyl;

-   rings B, B′ each independently signify phenylene which is    unsubstituted or optionally substituted with fluorine, chlorine,    cyano, alkyl or alkoxy, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4-    or 2,6-naphthylene, 1,3-dioxane-2,5-diyl, cyclohexane-1,4-diyl;

-   Y¹, Y², Y^(1′), Y^(2′) each independently signify a single covalent    bond, —(CH₂)_(t)—, —O—, —CO—, —CO—O—, —O—OC—, —CF₂O—, —OCF₂—, —NR⁴—,    —CO—NR⁴—, —R⁴N—CO—, —(CH₂)_(u)—O—, —O—(CH₂)_(u)—, —(CH₂)_(u)—NR⁴— or    —NR⁴—(CH₂)_(u)—, in which

-   R⁴, R^(4′) each independently signify hydrogen or lower alkyl;

-   t, t′ each independently signify a whole number of 1 to 4;

-   u, u′ each independently signify a whole number of 1 to 3;

-   rings C, C′ each independently signify phenylene which is    unsubstituted or optionally substituted with fluorine, chlorine,    cyano, alkyl or alkoxy, or pyrimidine-2,5-diyl, pyridine-2,5-diyl,    2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene;

-   Z, Z′ each independently signify —O— or —NR⁵—, in which R⁵ signifies    hydrogen or lower alkyl, or a second group of formula D, in which

-   D, D′ each independently signify hydrogen or a straight-chain or    branched alkylene group with 1 to 20 carbon atoms which is    optionally substituted with fluorine or chlorine, a cycloalkyl    residue with 3 to 8 ring atoms which is optionally substituted with    fluorine, chlorine, alkyl or alkoxy.

-   M² signifies a repeating monomer unit from the group; acrylate,    methacrylate, 2-chloroacrylate, 2-phenylacrylate; optionally N-lower    alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide and    2-phenylacrylamide; vinyl ether, vinyl ester; straight-chain or    branched alkyl esters of acrylic or methacrylic acid, allyl esters    of acrylic or methacrylic acid, alkyl vinyl ethers or esters,    phenoxyalkyl acrylates or phenoxyalkyl methacrylates, phenylalkyl    acrylates or phenylalkyl methacrylates, hydroxyalkyl acrylates or    hydroxyalkyl methacrylates with alkyl residues of 1 to 20,    preferably 1 to 10, especially however with 1 to 6, carbon atoms;    acrylonitrile, methacrylonitrile, styrene, 4-methylstyrene,    siloxane; and

-   w, w and w² are molar fractions of the comonomers with 0<w<1, 0<w¹<1    and 0<w²≤0.5.

Preferred are polymer material with repeating units of formula (Ia),wherein M¹, S¹, M^(1′), S^(1′), M² and m, n, m′, n′ are as defined asabove; and rings A, A′

each independently signify phenylene which is unsubstituted oroptionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy,pyridine-2,5-diyl, pyrimidine-2,5-diyl, cyclohexane-1,4-diyl; rings B,B′ each independently signify phenylene which is unsubstituted oroptionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy,pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4- or 2,6-naphthylene orcyclohexane-1,4-diyl; Y¹, Y², Y^(1′), Y^(2′) each independently signifya single covalent bond, —CH₂CH₂—, —O—, —CH₂—O—, —O—CH₂—, —CF₂O—, —OCF₂—,—CO—O— or —O—OC—; rings C, C′each independently signify phenylene which is unsubstituted oroptionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy,or pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-furanylene or 1,4- or2,6-naphthylene; Z, Z′ signify —O— and D, D′ each independently signifya straight-chain or branched alkylene group with 1 to 20, carbon atoms,preferably 1 to 12 carbon atoms or a cycloalkyl residue with 5 to 6 ringatoms which is optionally substituted with alkyl or alkoxy, especiallywith methyl or methoxy; and w, w¹ and w² are molar fractions of thecomonomers with 0<w<1, 0<w¹<1 and 0<w²≤0.5.

Especially preferred are polymer with repeating units of formula (Ia),wherein M¹, S¹, M^(1′), S^(1′), M² and m, n, m′, n′; and rings B, B′each independently signify phenylene which is unsubstituted oroptionally substituted with fluorine, chlorine, cyano, alkyl or alkoxy,pyridine-2,5-diyl, pyrimidine-2,5-diyl or cyclohexane-1,4-diyl;

-   Y², Y^(2′) each independently signify a single covalent bond, —CO—O—    or —O—OC—;-   m, m′ each independently signify 0 or 1;-   n, n′ signify 0;-   rings C, C each independently signify phenylene which is    unsubstituted or optionally substituted with fluorine, chlorine,    cyano, alkyl or alkoxy or 1,4- or 2,6-naphthylene;-   Z, Z′ signifiy —O— and-   D, D′ each independently signify hydrogen or a straight-chain or    branched alkylene group with 1 to 12 carbon atoms; and-   w, w¹ and w² are molar fractions of the comonomers with 0<w<1,    0<w¹<1 and 0<w²≤0.5.

Further preferred polymer material of formula (I) containing structureswhich are usual in polymer chemistry consist of compounds of the formula(Ib),

wherein

-   M¹, M², S¹, A, B, C, D, Z, Y¹, Y², m and n are as defined above, and-   w and w² are molar fractions of the comonomers with 0<w<1 and    0<w²≤0.5.

Preferred are copolymer compositions with repeating units of formula(Ib), wherein M¹, M² and S¹ are as defined above; and

-   ring A signifies phenylene which is unsubstituted or optionally    substituted with fluorine, chlorine, cyano, alkyl or alkoxy,    pyridine-2,5-diyl, pyrimidine-2,5-diyl, cyclohexane-1,4-diyl;-   ring B signifies phenylene which is unsubstituted or optionally    substituted with fluorine, chlorine, cyano, alkyl or alkoxy,    pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4- or 2,6-naphthylene or    cyclohexane-1,4-diyl;-   Y¹, Y² each independently signify a single covalent bond, —CH₂CH₂—,    —O—, —CH₂—O—, —O—CH₂—, —CO—O— or —O—OC—;-   m, n each independently signify 0 or 1;-   ring C signifies phenylene which is unsubstituted or optionally    substituted with fluorine, chlorine, cyano, alkyl or alkoxy, or    pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-furanylene or 1,4- or    2,6-naphthylene;-   Z signifies —O—, and-   D signifies hydrogen or a straight-chain or branched alkylene group    with 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a    cycloalkyl residue with 5 to 6 ring atoms which is optionally    substituted with alkyl or alkoxy, especially with methyl or methoxy;    and-   w and w² are molar fractions of the comonomers with 0<w<1 and    0<w²≤0.5.

Especially preferred are copolymer material comprising repeating unitsof formula (Ib), wherein n signifies 0 and M¹, M² and S¹ are as definedabove; and

-   ring B signifies phenylene which is unsubstituted or optionally    substituted with fluorine, chlorine, cyano, alkyl or alkoxy,    pyridine-2,5-diyl, pyrimidine-2,5-diyl or cyclohexane-1,4-diyl;-   Y² signifies a single covalent bond, —CO—O— or —O—OC—;-   m signifies 0 or 1; n signifies 0;-   ring C signifies phenylene which is unsubstituted or optionally    substituted with fluorine, chlorine, cyano, alkyl or alkoxy or 1,4-    or 2,6-naphthylene;-   Z signifies —O— and-   D signifies hydrogen or a straight-chain or branched alkylene group    with 1 to 12 carbon atoms, and w and w² are molar fractions of the    comonomers with 0<w<1 and 0<w²≤0.5.

One such preferred copolymer material with structures of formula (Ib)which are usual in polymer chemistry are:

-   poly[1-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-6-hexyloxycarbonyl]-1-methyl-ethylene-co-1-[1-hydroxy-butoxyoxycarbonyl]-1-methyl-ethylene];-   poly[1-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-oxy-6-hexyloxycarbonyl]-1-methyl-ethylene-co-1-[2-ethylhexyloxycarbonyl]-1-methyl-ethylene];-   poly[1-[4-[2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-phenoxy]-oxy-8-octyloxycarbonyl]-1-methyl-ethylene-co-1-ethoxycarbonyl-1-methyl-ethylene];-   poly[1-[4-[2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-phenoxy]-oxy-8-octyloxycarbonyl]-1-methyl-ethylene-co-1-[2-ethylhexyloxycarbonyl-1-methyl-ethylene],-   poly[1-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-oxy-6-hexyloxycarbonyl]-1-methyl-ethylene-co-1-ethoxycarbonyl-1-methyl-ethylene].-   poly[1-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-oxy-6-hexyloxycarbonyl]-1-methyl-ethylene-co-1-[2-hydroxy-ethoxycarbonyl]-1-methyl-ethylene];    -   Further preferred polymer material of formula I consists of        compounds with repeating units of formula (Ic),

-   -   wherein    -   M¹, S¹, A, B, C, D, Z, Y¹, Y², m and n as well as M^(1′),        S^(1′), A′, B′, C′, D′, Z′, Y^(1′), Y^(2′), m′ and n′ are as        defined above; and w and w¹ are molar fractions of the        comonomers with 0<w<1 and 0<w¹<1.

Preferred are copolymer compositions with repeating units of formula Ic,wherein M¹ and S¹ as well as M^(1′) and S^(1′) as well as m, n, m′, n′are as defined above; and rings A, A′

-   each independently signify phenylene which is unsubstituted or    optionally substituted with fluorine, chlorine, cyano, alkyl or    alkoxy, pyridine-2,5-diyl, pyrimidine-2,5-diyl,    cyclohexane-1,4-diyl;-   rings B, B′ each independently signify phenylene which is    unsubstituted or optionally substituted with fluorine, chlorine,    cyano, alkyl or alkoxy, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4-    or 2,6-naphthylene or cyclohexane-1,4-diyl; Y¹, Y², Y^(1′), Y^(2′)-   each independently signify a single covalent bond, —CH₂CH₂—, —O—,    —CH₂—O—, —O—CH₂—, —OCF₂—, —CF₂O—, CO—O— or —O—OC—;-   rings C, C′ each independently signify phenylene which is    unsubstituted or optionally substituted with fluorine, chlorine,    cyano, alkyl or alkoxy, or pyrimidine-2,5-diyl, pyridine-2,5-diyl,    2,5-furanylene or 1,4- or 2,6-naphthylene;-   Z, Z′ signify —O— and-   D, D′ each independently signify a straight-chain or branched    alkylene group with 1 to 20, carbon atoms, preferably 1 to 12 carbon    atoms or a cycloalkyl residue with 5 to 6 ring atoms which is    optionally substituted with alkyl or alkoxy, especially with methyl    or methoxy; and-   w and w¹ are molar fractions of the comonomers with 0<w<1 and    0<w¹<1.

Especially preferred are copolymer material comprises with repeatingunits of formula (Ic), wherein n and n′ signify 0 and M¹ and S¹ as wellas M^(1′) and S^(1′) and m, m′ are as defined above; and

-   rings B, B′ each independently signify phenylene which is    unsubstituted or optionally substituted with fluorine, chlorine,    cyano, alkyl or alkoxy, pyridine-2,5-diyl, pyrimidine-2,5-diyl or    cyclohexane-1,4-diyl;-   Y², Y^(2′) each independently signify a single covalent bond, —CO—O—    or —O—OC—;-   rings C, C′ each independently signify phenylene which is    unsubstituted or optionally substituted with fluorine, chlorine,    cyano, alkyl or alkoxy or 1,4- or 2,6-naphthylene;-   Z, Z′ signify —O— and-   D, D′ each independently signify hydrogen or a straight-chain or    branched alkylene group with 1 to 12 carbon atoms; and-   w and w¹ are molar fractions of the comonomers with 0<w<1 and    0<w¹<1.

One such preferred copolymer material of formula (I) comprises compoundswith repeating units of formula (Ic), namely

-   poly[1-[4-[2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]]-oxy-6-hexyloxycarbonyl]-1-methyl-ethylene    or-   poly[1-[4-[2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-phenoxy]-oxy-6-hexyloxycarbonyl]-1-methyl-ethylene.

Preferred is copolymer material of the formula (Ia).

Especially preferred is copolymer material of the formulae (Ib) and(Ic).

Quite especially preferred is homopolymer material.

Homopolymer material comprising repeating units of formula (I) arepreferred,

-   -   wherein    -   M¹, S¹, A, B, C, D, Z, Y¹, Y², m and n are as defined above.

Preferred homopolymer is

-   poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]]-6-hexyloxy]-1-methyl-ethylene,    2-Propenoic acid, 2-methyl-,    6-[4-[(1E)-3-methoxy-3-oxo-1-propen-1-yl]phenoxy]hexyl ester,    homopolymer.

Especially preferred are homopolymer material comprising repeating unitsof formula (I), wherein

-   M¹, S¹ and m, n are as defined as above; and-   ring A signifies phenylene which is unsubstituted or optionally    substituted with fluorine, chlorine, cyano, alkyl or alkoxy,    pyridine-2,5-diyl, pyrimidine-2,5-diyl, cyclohexane-1,4-diyl;-   ring B signifies phenylene which is unsubstituted or optionally    substituted with fluorine, chlorine, cyano, alkyl or alkoxy,    pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4- or 2,6-naphthylene or    cyclohexane-1,4-diyl;-   Y¹, Y² each independently signify a single covalent bond, —CH₂CH₂—,    —O—, —CH₂—O—, —O—CH₂—, —CO—O—, —O—OC—, —CF₂—O— or —O—F₂C—;-   ring C signifies phenylene which is unsubstituted or optionally    substituted with fluorine, chlorine, cyano, alkyl or alkoxy, or    pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-furanylene or 1,4- or    2,6-naphthylene;-   Z signifies —O—, and-   D signifies hydrogen or a straight-chain or branched alkylene group    with 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a    cycloalkyl residue with 5 to 6 ring atoms which is optionally    substituted with alkyl or alkoxy, especially with methyl or methoxy.

Especially preferred are homopolymer compositions with repeating unitsof formula I, wherein n signifies 0 and

-   M¹ and S¹ are as defined above; and    -   ring B signifies phenylene which is unsubstituted or optionally        substituted with fluorine, chlorine, cyano, alkyl or alkoxy,        pyridine-2,5-diyl, pyrimidine-2,5-diyl or cyclohexane-1,4-diyl;    -   Y² signifies a single covalent bond, —CO—O— or —O—OC—;-   m signifies 0 or 1; n signifies 0;-   ring C signifies phenylene which is unsubstituted or optionally    substituted with fluorine, chlorine, cyano, alkyl or alkoxy or 1,4-    or 2,6-naphthylen;-   Z signifies —O—, and-   D signifies hydrogen or a straight-chain or branched alkylene group    with 1 to 12 carbon atoms.

Especially preferred homopolymer composition include

-   poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-hexoxycarbonyl]-1-methyl-ethylene],    2-Propenoic acid, 2-methyl-,    6-[4-[(1E)-3-methoxy-3-oxo-1-propen-1-yl]phenoxy]hexyl ester,    homopolymer.

The polymers of formula I are characterized by being readily accessible.The methods for the production are known to a person skilled in the art.

The present invention relates to a process for the preparation ofpolymer material of formula (I) comprising reacting the monomer compoundof formula (I′).

The polymers of formula (I) can be prepared in principal according totwo different processes. In addition to the direct polymerization ofpre-finished monomers there exists the possibility of polymer-analogousreaction of reactive cinnamic acid derivatives with functional polymers.

For the direct polymerization, the monomers and the comonomers arefirstly prepared separately from the individual components. Theformation of the polymers is subsequently effected in a manner known perse under the influence of UV radiation or heat or by the action ofradical or ionic catalysts. Potassium peroxodisulphate, dibenzoylperoxide, azobisisobutyronitrile or di-tert.-butylperoxide are examplesof radical initiators. Ionic catalysts are alkali-organic compounds suchas phenyllithium or naphthylsodium or Lewis acids such as BF₃, AlCl₃,SnCl₃ or TiCl₄. The monomers can be polymerized in solution, suspension,emulsion or substance.

Solvents which are used in the preparation of the polymers according tothe invention are as defined above.

In the second process a polymer of formula (I) can also be produced in apolymer-analogous reaction from a pre-finished functional polymer and asuitable functionalized cinnamic acid derivative. Many known processessuch as, for example, esterification, trans-esterification, amidation orthe etherification are suitable for polymer-analogous reactions.

The etherification of hydroxycinnamic acid derivatives withpolyhydroxyalkyl acrylates or polyhydroxyalkyl methacrylates in solutionunder the conditions of the Mitsunobu reaction has been found to beadvantageous here. Thus, the reaction can be carried out, for example,in that all hydroxy groups are reacted (homopolymer) or in that afterthe reaction hydroxy groups are still free on the polymer, which canthen be further functionalized in a further polymer-analogous reaction,by which means copolymers can be synthesized. An alternative possibilityfor the production of copolymers according to this process comprisesusing mixtures of different cinnamic acid derivatives.

The cinnamic acids are partially commercially available or can beobtained according to methods known in the literature such as, forexample, the Knoevenagel reaction or the Wittig reaction fromcommercially available aldehydes or from cyano compounds which areobtained by previous reduction to the corresponding aldehydes. Thecinnamic esters or amides can then be prepared from the cinnamic acidsaccording to known esterification procedures.

The polymer of formula (I) is in general applied in form of acomposition, especially a formulation or blend.

Hence, the present invention further comprises a composition comprisinga polymer material of formula (I) and optionally a solvent within themeaning and preferences as given above for solvents,

-   -   in addition optionally further additives, such as    -   silane-containing compounds or/and    -   epoxy-containing crosslinking agents or/and    -   photo-sensitizers, or/and    -   photo-radical generators, or/and    -   cationic photo-initiators, or/and    -   surfactants, or/and    -   emulsifiers, or/and    -   antioxidant, or/and    -   leveling agent.

Suitable silane-containing additives are described in Plast. Eng. 36(1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc.

Suitable epoxy-containing cross-linking additives include

4,4′-methylene-bis-(N,N-diglycidylaniline), trimethylolpropanetriglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid1,2,4,5-N,N′-diglycidyldiimide, polyethylene glycol diglycidyl ether,N,N-diglycidylcyclohexylamine and the like.

Suitable photo-active additives include 2,2-dimethoxyphenylethanone, amixture of diphenylmethanone and N,N-dimethylbenzenamine or ethyl4-(dimethylamino)benzoate, xanthone, thioxanthone, Irgacure® 184, 369,500, 651 and 907 (Ciba), Michler's ketone, triaryl sulfonium salt andthe like.

The present invention also relates to the use of the polymer materialscomprising repeating units of formula (I) as orienting layer for liquidcrystals.

Further, the present invention relates to a method for the preparationof an orientation layer for liquid crystals comprising irradiatingpolymer material which comprises repeating units of formula (I) or thecomposition comprising polymer material which comprises repeating unitsof formula (I) with aligning light.

Preferably method comprises

-   -   applying a composition comprising a polymer material of        formula (I) within the meaning and preferences as described        above to a carrier,    -   and irradiating the polymer material which comprises repeating        units of formula (I) or the composition comprising polymer        material which comprises repeating units of formula (I) with        aligning light.

Especially preferred is the method, wherein two irradiation processesare conducted one with aligning light and the other with or withoutaligning light, such as isotropic light.

The term “carrier” as used in the context of the present invention ispreferably transparent or not-transparent, preferably glass or plasticsubstrates, polymer films, such as polyethyleneterephthalat (PET),tri-acetyl cellulose (TAC), polypropylen, optionally coated with indiumtin oxide (ITO), however not limited to them.

In general the composition is applied by general coating and printingmethods known in the art. Coating methods are for example spin coating,air doctor coating, blade coating, knife coating, reverse-roll coating,transfer roll coating, gravure roll coating, kiss roll coating, castcoating, spray coating, slot-orifice coating, calendar coating,electrodepositing coating, dip coating or die coating.

Printing methods are for example relief printing such as flexographicprinting, ink jet printing, intaglio printing such as direct gravureprinting or offset gravure printing, lithographic printing such asoffset printing, or stencil printing such as screen printing.

In the context of the present invention, “aligning light” is light ofwavelengths, which can initiate photoreaction, especially which caninduce anisotropy in the photoalignment layer of (I). Preferably, thewavelengths are in the UV-A, UVB and/or UV/C-range, or in the visiblerange. It depends on the photoalignment compound, which wavelengths areappropriate. Preferably, the photo-reactive groups are sensitive tovisible and/or UV light. A further embodiment of the invention concernsthe generating of aligning light by laser light.

The UV light is preferably selected according to the absorption of thephoto-reactive groups, i.e. the absorption of the film should overlapwith the emission spectrum of the lamp used for the LP-UV irradiation,more preferably with linearly polarized UV light. The intensity and theenergy used are chosen depending on the photosensitivity of the materialand on the orientation performances which are targeted. In most of thecases, very low energies (few mJ/cm2) already lead to high orientationquality.

More preferably, “aligning light” is at least partially linearlypolarized, elliptically polarized, such as for example circularlypolarized, or non-polarized, most preferably circularly polarized, ornon-polarized light exposed obliquely, or at least partially linearlypolarized light. Especially, most preferred aligning light denotessubstantially polarised light, especially linearly polarised light; oraligning light denotes non-polarised light, which is applied by anoblique irradiation.

More preferably, the aligning light is UV light, preferably linearlypolarized UV light.

Thus, for the production of orienting layers in regions which arelimited selectively by area, a solution of the polymer material obtainedcan applied. For example, firstly be produced and can be spun in aspin-coating apparatus on to a carrier which is optionally coated withan electrode (for example, a glass plate coated with indium-tin oxide(ITO) such that homogeneous layers of 0.05-50 μm thickness result.Subsequently, the regions to be oriented can be exposed e.g. to amercury high-pressure lamp, a xenon lamp or a pulsed UV laser using apolarizer and optionally a mask in order to form structures. Theduration of the exposure depends on the output of the individual lampsand can vary from a few minutes to several hours. The photoreaction can,however, also be effected by irradiating the homogeneous layer usingfilters which let through e.g. only the radiation which is suitable forthe photo reaction.

A preferred method of the invention relates to processes for thepreparation of an orienting layer wherein the time is a criticalparameter, especially in which the irradiation time is a criticalparameter, such as especially to a roll-to-roll process.

The present invention also relates to orientation layers comprising apolymer material which comprises repeating units of formula (I) or acomposition comprising said polymer material.

The use of the polymers in accordance with the invention as orientinglayers for liquid crystals as well as their use in of non-structured andstructured optical and electro-optical components, especially for theproduction of hybrid layer elements, is also objects of the presentinvention.

Further, the present invention relates to optical or electro-opticalelements comprising polymer material (I) or/and a composition comprisingpolymer material (I) or/and an orientation layer prepared by usingpolymer material (I).

The term “structured” refers to a variation in the azimuthalorientation, which is induced by locally varying the direction of thepolarized aligning light.

In addition, the present invention relates to the use of the polymermaterial according to the present invention as an orienting layer, foraligning organic or inorganic compounds, especially for aligning liquidcrystals and liquid crystal polymers.

The present invention also relates to the use of the orienting layer ofthe invention in the manufacture of optical or electro-optical componentand systems, especially multilayer systems, or devices for thepreparation of

a display waveguide, a security or brand protection element, a bar code,an optical grating, a filter, a retarder, such as 3D-retarder films, acompensation film, a reflectively polarizing film, an absorptivepolarizing film, an anisotropically scattering film compensator andretardation film, a twisted retarder film, a cholesteric liquid crystalfilm, a guest-host liquid crystal film, a monomer corrugated film, asmectic liquid crystal film, a polarizer, a piezoelectric cell, a thinfilm exhibiting non linear optical properties, a decorative opticalelement, a brightness enhancement film, a component forwavelength-band-selective compensation, a component for multi-domaincompensation, a component of multiview liquid crystal displays, anachromatic retarder, a polarization state correction/adjustment film, acomponent of optical or electro-optical sensors, a component ofbrightness enhancement film, a component for light-basedtelecommunication devices, a G/H-polarizer with an anisotropic absorber,a reflective circular polarizer, a reflective linear polarizer, a MC(monomer corrugated film), liquid crystal displays, especially twistednematic (TN) liquid crystal displays, hybrid aligned nematic (HAN)liquid crystal displays, electrically controlled birefringence (ECB)liquid crystal displays, supertwisted nematic (STN) liquid crystaldisplays, optically compensated birefringence (OCB) liquid crystaldisplays, pi-cell liquid crystal displays, in-plane switching (IPS)liquid crystal displays, fringe field switching (FFS) liquid crystaldisplays, vertically aligned (VA) liquid crystal displays; all abovedisplay types are applied in either transmissive or reflective ortransflective mode.

The optical or electro-optical component and systems, especiallymultilayer systems and devices can be patterned or unpatterned.

The term patterning preferably denotes to birefringence patterningand/or thickness patterning and/or patterning of the optical axisorientation, and/or patterning of the degree of polymerization.Birefringence denotes the difference between the extra-ordinary and theordinary index of refraction.

Thus the invention further relates to an optical or electro-opticalelements, systems and devices device comprising polymer material orcomposition comprising said polymer material within the above givenmeaning and preferences.

Preferred are optical or electro-optical elements, systems and devicescomprising orienting layers according to the present invention and atleast one orientable layer, such as a liquid crystal layer or liquidcrystal polymer layer.

An optical component, system or device creates, manipulates, or measureselectromagnetic radiation.

An electro-optical component, system or device operates by modificationof the optical properties of a material by an electric field. Thus itconcerns the interaction between the electromagnetic (optical) and theelectrical (electronic) states of materials.

The orienting material has the ability to align compounds, such as forexample liquid crystals, such as nematic liquid crystals, with theirlong axis along a preferred direction.

The present invention also relates to the use of the orienting layeraccording to the present invention, for aligning organic or inorganiccompounds, especially for aligning liquid crystals.

The term “anisotropy” or “anisotropic” refers to the property of beingdirectionally dependent. Something which is anisotropic may appeardifferent or have different characteristics in different directions.

Preferred is the use for the induction of planar alignment, tilted orvertical alignment of adjacent liquid crystalline layers; more preferredis the use for the induction of planar alignment or vertical alignmentin adjacent liquid crystalline layers.

It has surprisingly been found in the present invention that side-chainpolymers (I) having an elongated spacer unit have fast orientation andare therefore give access to efficient manufacturing processes such asespecially roll-to-roll processes. The materials show good orientationproperties such as high contrast. They also allow short irradiationtimes for aligning at almost low energies. Very advantageous it wasfound that these materials can be coated on several substrates such asglass, or flexible substrates such as PET or TAC and herewith lead tohuge palette of applicatory possibilities.

In addition, the polymers in accordance with the invention show asubstantially better orientation of the liquid crystals.

The polymers in accordance with the invention are illustrated in moredetail by the following Examples. In the Examples hereinafter T_(g)signifies the glass temperature, ε signifies the molar decadicabsorption coefficient, G signifies a glassy solidification, C signifiesthe crystalline phase, S signifies the smectic phase, N signifies thenematic phase and I signifies the isotropic phase, p signifies thenumber of repeating units resulting in polymers having a molecularweight M_(W) between 1,000 and 5,000,000, preferably however between5,000 and 2,000,000, especially advantageously however between 10,000and 1,000,000, w, w¹ and w² are molar fractions of the comonomers with0<w<1.0<w¹<1 and 0<w²≤0.5.

EXAMPLE 1Poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-hexoxycarbonyl]-1-methyl-ethylene],which is 2-Propenoic acid,2-methyl-,6-[4-[(1E)-3-methoxy-3-oxo-1-propen-1-yl]phenoxy]hexyl ester,homopolymer

-   -   0.73 g (2.03 mmol) of        6-{4-[(1E)-3-methoxy-3-oxoprop-1-enyl]phenoxy}hexyl        (2Z)-2-methylbut-2-enoate and 1.67 mg (0.01 mmol) of        2,2′-azo-bis-isobutyronitrile (AIBN) are dissolved in 4.1 ml of        tetrahydrofuran (THF). The solution is flushed with a weak        stream of argon for 15 minutes. Subsequently, the reaction        vessel is sealed air-tight and heated to 60° C. After 24 hours        the vessel is opened, the solution is diluted with 4 ml of THF        and is added drop wise to 800 ml of diethyl ether at room        temperature while stirring vigorously. The separated polymer is        filtered off and dried at 60° C. in a water-jet vacuum. For        further purification, the polymer is dissolved in 10 ml of        dichloromethane and again precipitated in 80 ml of diethyl        ether. This procedure is repeated until monomer is no longer        detected by thin-layer chromatography. Filtration and drying at        60° C. in a vacuum gives 0.37 g of product        poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-hexoxycarbonyl]-1-methyl-ethylene];        as a white powder with a glass stage at T_(g)=11° C. and a        decadic absorption maximum of λ_(max.) (in CH₂Cl₂)=309 nm        (ε=36000 l/mol cm).

¹H-NMR (in CDCl₃): 1.730, 1.610, 1.562, 1.4-1 ppm (5×CH₂ and CH₃), 3.75ppm (OOCH₃), 3.89-3.88 ppm (2×OCH₂), 6.27 and 6.23 and 7.60 and 7.56 ppm(CH═CH)

The 6-[4-[(E)-2-Methoxycarbonyl-vinyl]-phenoxy]-hexyl 2-methyl-acrylateused as starting material is prepared according to the followingprocedure.

Methyl 3-(4-hydroxyphenyl)-acrylate

51.2 g (312 mmol) of p-coumaric acid are dissolved in 330 ml of methanoland treated with 10 ml of concentrated sulphuric acid. The solution isheated under reflux for 2 hours. Subsequently the majority of themethanol (about 200 ml) is distilled off and the residue remainingbehind was poured into 1.3 l of ice-water. The separated ester isfiltered off under suction and washed in succession with cold water,with a small amount of cold NaHCO₃ solution and again with cold water.Drying at 50° C. in a water-jet vacuum gives 51.1 g of methyl3-(4-hydroxyphenyl)-acrylate in the form of a light brownish colouredpowder.

Methyl (E)-3-[4-[6-hydroxyhexoxy]-phenyl]-acrylate

30 g (168 mmol) of methyl 3-(4-hydroxyphenyl)-acrylate, 29 g (210 mmol)of anhydrous K₂CO₃ and a spatula tip of KI are placed in 200 ml ofdimethylformamide. 17.95 g (185 mmol) of 6-chlorohexanol are added dropwise at 85° C. within 5 minutes while stirring. The batch is stirred at85° C. for a further 3 days. Subsequently, the salts are filtered offand the filtrate is concentrated to dryness in a water-jet vacuum. 17.2g of methyl (E)-3-[4-[6-hydroxyhexoxy]-phenyl]-acrylate are obtained inthe form of white crystals after recrystallization from i-propanol.

6-[4-[(E)-2-Methoxycarbonyl-vinyl]-phenoxy]-hexyl 2-methyl-acrylate

-   -   2.56 g (30 mmol) of methacrylic acid in 10 ml of THF are slowly        added drop wise to a solution of 6.1 g (27 mmol) of methyl        (E)-3-[4-[6-hydroxyhexoxy]-phenyl]-acrylate, 5.85 g (28.3 mmol)        of N,N′-dicyclohexylcarbodiimide (DCC) and 0.37 g (3 mmol) of        4-dimethylamino-pyridine in 80 ml of tetrahydrofuran (THF). The        batch is stirred at room temperature overnight. In order to        complete the reaction there are added firstly a further 1.46 g        (7.1 mmol) of DCC and, after stirring for one hour, a further        0.5 g (5.9 mmol) of methacrylic acid. The batch is stirred for a        further 24 hours, filtered and the filtrate is extracted 3 times        each time with 200 ml of 5% acetic acid and 200 ml of water. The        ether phase is dried over Na₂SO₄, evaporated and the residue is        recrystallized from cyclohexane. Subsequently, the still        slightly impure product is filtered over a thin silica gel layer        (eluent: diethyl ether/hexane=1:1). This gives 8.1 g of        6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-hexyl        2-methyl-acrylate as a white powder, having a melting point of        45-50° C. and a decadic absorption maximum of λ_(max.) (in        CH₂Cl₂)=310 nm (ε=37000 l/mol cm).    -   The following polymers are synthesized in an analogous manner:

-   poly[1-[6-[4-[(E)-2-ethoxycarbonyl-vinyl]-phenoxy]-hexoxycarbonyl]-1-methyl-ethylene];

-   poly[1-[3-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-propoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=306 nm

-   poly[1-[4-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-butoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=307 nm

-   poly[1-[5-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-pentoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=309 nm

-   poly[1-[7-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-heptoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=309 nm

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-octoxycarbonyl]-1-methyl-ethylene];    T_(g)=21.4° C.;

-   poly[1-[9-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-undecoxycarbonyl]-1-methyl-ethylene];

-   poly[1-[4-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxyphenoxy]-butoxycarbonyl]-1-methyl-ethylene];    T_(g)=60° C.; λ_(max.) (in CH₂Cl₂)=322.5 and 295.5 nm

-   poly[1-[5-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxyphenoxy]-pentoxycarbonyl]-1-methyl-ethylene];

-   poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxyphenoxy]-hexoxycarbonyl]-1-methyl-ethylene];    T_(g)=64° C.;

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxyphenoxy]-octoxycarbonyl]-1-methyl-ethylene];

-   poly[1-[11-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxyphenoxy]-undecoxycarbonyl]-1-methyl-ethylene];

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-octoxy]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=309 nm

-   poly[1-[2-[4-[(E)-2-methoxycarbonyl-vinyl]-phenyl    carbonyloxy]-ethoxycarbonyl]-1-methyl-ethylene];

-   poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenyl    carbonyloxy]-hexoxycarbonyl]-1-methyl-ethylene]; T_(g)=29.8° C.;

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenyl    carbonyloxy]-octoxycarbonyl]-1-methyl-ethylene]

-   poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-hexoxycarbonyl]-1-methyl-ethylene-co-[4-hydroxybutoxycarbonyl]-ethylene]

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-2-octoxy-phenoxy]-octoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=323 nm (ε=17829 l/mol cm),

-   poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-hexoxycarbonyl]-1-methyl-ethylene-co-[4-hydroxybutoxycarbonyl]-ethylene],    T_(g)=28.5° C.;

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-(4-hexyl)-octoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=309 nm

-   poly[1-[1-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxy-phenoxy]-dec-1-ine-oxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=333 nm

-   poly[1-[3-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-(2-(4-butyloxyphenyl)-propoxycarbonyl)]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=308 nm

-   poly[1-[[3-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-(2-(4-butyloxyphenyl)-propyl)-1-carbamat-ethoxycarbonyl)]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=309 nm

-   poly[1-[[3-[(E)-2-methoxycarbonyl-vinyl]-2-methoxy-phenoxy]-(2-(4-butyloxphenyl)-propyl)-carbamat-ethoxycarbonyl)]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=322 nm

-   poly[1-[6-[4-[(E)-2-(adamantylmethoxycarbonyl-vinyl]-2-methoxy-phenoxy]-hexoxycarbonyl]-1-methyl-ethylene];    T_(g)=70° C.;

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-(2-(8-(5,5-dimethyl-1,3-dioxan-2-yl)    octyl)-propoxycarbonyl)]-1-methyl-ethylene]; λ_(max.) (in    CH₂Cl₂)=308 nm

-   poly[1-[[3-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-(3(2-(8-(5,5-dimethyl-1,3-dioxan-2-yl)-propyl)-carbamat-ethoxycarbonyl)]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=309 nm

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-2-(1-butyl-4-hexyl)-octoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=309 nm

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxy-phenoxy]-hex-1-ine-oxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=330 nm

-   poly[1-[[1-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-(propyl-3-((cyclopentyl-2-pentyl)-3-propxycarbonyl)]-1-methyl-ethylene];

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-2-(1-hexyl-6-oxymethyl)-octoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=310 nm

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-2-(1-ethyl)-octoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=310 nm

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxy-phenoxy]-dec-2-ene-oxycarbonyl]-1-methyl-ethylene];

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxyphenoxy]-2-(1-octyl)-octoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=324 nm

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-2-(1-octyl)-octoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=310 nm

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-2-(1-hexyl)-octoxycarbonyl]-1-methyl-ethylene];

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-3-(1-octyl)-octoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=309 nm

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-2-(1-butyl)-octoxycarbonyl]-1-methyl-ethylene];    λ_(max.) (in CH₂Cl₂)=299 nm

-   poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxyphenoxy]-2-(1-hexyl)hexoxycarbonyl]-1-methyl-ethylene]

-   poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-2-methoxyphenoxy]-2-(1-butyl)-octoxycarbonyl]-1-methyl-ethylene];    T_(g)=28.5° C.;

EXAMPLE 2Poly[1-[9-[4-[2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-phenoxy]-nonyloxycarbonyl]-1-methyl-ethylene]

-   -   2.5 g (5 mmol) of        2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenyl        4-[9-(2-methyl-acryloyloxy)-nonyloxy]-benzoate and 8.2 mg (0.05        mmol) of 2,2′-azo-bis-isobutyronitrile are dissolved in 10 ml of        tetrahydrofuran (THF). The solution is flushed with a weak        stream of argon for 30 minutes. Subsequently, the reaction        vessel is sealed air-tight and heated to 55° C. After 24 hours        the vessel is opened, the solution is diluted with 8 ml of THF        and is added drop wise to 1.6 of ethanol at room temperature        while stirring vigorously. The separated polymer is filtered off        and dried at 50° C. in a water-jet vacuum. For further        purification, the polymer is dissolved in about 25 ml of        dichloromethane and again precipitated in 1.75 of methanol. This        procedure is repeated until monomer is no longer detectable by        thin-layer chromatography. Filtration and drying at 50° C. in a        water-jet vacuum gave 2.1 g of        poly[1-[9-[4-[2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-phenoxy]-nonyloxycarbonyl]-1-methyl-ethylene]

The 2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenyl4-[9-(2-methyl-acryloyloxy)-nonyloxy]-benzoate used as the startingmaterial was prepared according to the following procedure:

4-(9-Hydroxy-nonyloxy)-benzoic acid

229.2 g (1.66 mol) of p-hydroxy-benzoic acid are dissolved in 600 ml ofmethanol and treated at 0° C. within 10 minutes with a solution of 151 g(3.77 mol) of NaOH in 480 ml of H₂O. 271.2 g (1.99 mol) of9-chloro-nonanol are slowly added dropwise to this solution. Finally,0.75 g of potassium iodide is added and the batch is boiled under refluxfor 60 hours. For the working up, the yellow solution is poured into 3of H₂O and treated with 10% HCl (about 600 ml) until a pH value of 1 hasbeen achieved. The milky suspension is filtered over a large suctionfilter. The residue is sucked dry and recrystallized twice from about1.5 of ethanol. This gives 230.6 g of 4-(9-hydroxy-nonyloxy)-benzoicacid as a fine white powder.

4-[9-(2-Methyl-acryloyloxy)-nonyloxy]-benzoic acid

88 g (0.3 mol) of 4-(9-hydroxy-nonyloxy)-benzoic acid and 101.5 g (1.18mol) of methacrylic acid are dissolved in 950 ml of chloroform. Afterthe addition of 7.2 g (0.07 mol) of hydroquinone and 7.2 g (0.04 mol) ofp-toluenesulphonic acid the batch is boiled under reflux on a waterseparator for 48 hours. The clear brown solution is subsequentlyevaporated, the residue is taken up in 1.5 of diethyl ether, filteredand shaken five time with 300 ml of H₂O each time. The organic phase isdried over Na₂SO₄, evaporated and the residue is recrystallized twicefrom methanol. After drying at 40° C. in a water-jet vacuum 48.2 g of4-[9-(2-methyl-acryloyloxy)-nonyloxy]-benzoic acid remained behind as awhite powder.

Methyl 4-hydroxy-3-methoxy-cinnamate

The preparation is effected analogously to Example 1 from 25 g (0.129mol) of 4-hydroxy-3-methoxy-cinnamic acid and 180 ml of methanol withconcentrated sulphuric acid as the catalyst. For purification, it ischromatographed on silica gel with dichloromethane/diethyl ether (19:1).This gives 21.78 g of methyl 4-hydroxy-3-methoxy-cinnamate as a paleyellow oil.

4-[(1E)-3-methoxy-3-oxoprop-1-enyl]-2-methylphenyl4-{[9-(methacryloyloxy)nonyl]oxy}benzoate

8.5 g (0.028 mol) of 4-[9-(2-methyl-acryloyloxy)-nonyloxy]-benzoate aretreated with 6 ml of thionyl chloride and 3 drops of DMF and the mixtureis heated to 90° C. for 2 hours. The excess thionyl chloride iscompletely removed firstly in a water-jet vacuum and subsequently in ahigh vacuum. The residual acid chloride is taken up in 20 ml ofdichloromethane and is slowly added dropwise at 0° C. to a solution of5.25 g (0.025 mol) of methyl 4-hydroxy-3-methoxy-cinnamate and 4.25 mlof triethylamine in 25 ml of THF. The batch is stirred at roomtemperature overnight, filtered and the filtrate is evaporated todryness. The residue is purified by column chromatography on silica gelwith dichloromethane/diethyl ether (19:1) and subsequently byrecrystallization from ethanol/THF. 6.31 g of2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenyl4-[9-(2-methyl-acryloyloxy)-nonyloxy]-benzoate are isolated as a whitepowder.

The following polymers are synthesized in an analogous manner:

-   Poly[1-[10-[4-[2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-phenoxy]-decyloxycarbonyl]-1-methyl-ethylene];-   Poly[1-[11-[4-[2-methoxy-4-[(E)-2-methoxycarbonyl-vinyl]-phenoxycarbonyl]-phenoxy]-undecyloxycarbonyl]-1-methyl-ethylene].

APPLICATION EXAMPLES

In the examples below, solutions of polymer materials according to theinvention are prepared and are used for coating thin layers of thepolymer material on a substrate.

The polymer-layers are then photo-aligned by exposure to linearlypolarized uv-light to generate an orientation layer. On top of eachphoto-aligned polymer-layer a layer of cross-linkable liquid crystalswas prepared, which after having been oriented by the orientation layerare uv cross-linked. The cross-linked liquid crystal (LCP-) layer isanalyzed by determination of the contrast ratio, which is a measure ofthe alignment quality.

The procedure for the preparation of solutions of the polymer material,orientation layers, LCP-layers and the measurement of contrast ratio aswell as the characterization of the LCP-layer is described below.

Preparation of a Solution of the Polymer Material (=Composition)

A solution of a polymer material is prepared by dissolving 2% by weightof the polymer material in cyclopentanone. The polymer solution isstirred for 30 minutes at room temperature.

Preparation of an Orientation Layer

A glass substrate is spin coated with the polymer solution at a spinningspeed of 3000 rpm for 1 minute. The coated substrate is then dried at180° C. for 10 minutes. The thickness of the resulting polymer-layer isabout 50 nm.

The polymer-layers are exposed to linearly polarized uv-light (LPUV) inthe wavelength range of 280 to 340 nm. The substrate area is segmentedinto 8 stripes, each of which is irradiated with a different LPUVenergy, namely 1, 2, 4, 8, 16, 32 and 64 up to 600 mJ/cm², in order tostudy the energy dependence of the orientation performance. Thepolarization direction is the same for all segments.

Preparation of LCP-Solutions

LCP-Solution S1: Mixture M1_(LCP), comprising cross-linkable liquidcrystals consisted of:

-   67.4% LC1-   19.2% LC2-   9.6% C1-   1.9% Irgacure® 369-   1.9% BHT, 4-methyl-2, di-tertiary butyl phenol

LCP-solution S1 is prepared by dissolving 15% by weight of mixtureM1_(LCP) in anisole and then stirring the solution for 30 minutes at 50°C.

LCP-Solution S2: Mixture M2_(LCP), comprising cross-linkable liquidcrystals consisted of:

-   77.0% LC1-   14.4% LC3-   4.8% LC4-   1.9% Irgacure® 369-   1.9% BT, 4-methyl-2, di-tertiary butyl phenol

LCP-solution S2 is prepared by dissolving 10% by weight of mixtureM2_(LCP) in Anisole and then stirring the solution for 30 minutes at 50°C.

Preparation of a LCP Layer Aligned by the Orientation Layer

An LCP layer is prepared on top of the orientation layer by spin-coatingthe respective LCP-solution at 1000 rpm for 2 minutes. The liquidcrystal layer is then annealed for 10 minutes at 50° C. and subsequentlythe liquid crystals are cross-linked at room temperature in nitrogenatmosphere by irradiation with UV-A light of 2 mW/cm² for 5 minutes.

Measurement of Contrast Ratio

Contrast ratio is measured with a polarizing microscope, equipped with aphoto-multiplier as a light sensor. Measurements are done with thepolarizers in crossed position. The substrate with the birefringentLCP-layer is fixed on a rotatable sample holder. For determination ofthe contrast ratio two measurements are performed. For the firstmeasurement the sample is rotated to the position with the lowestintensity measured by the photo-multiplier. In this position the opticalaxis is parallel to one of the polarizers and the measured intensity isdefined as the dark state intensity. Then the sample is rotated by 45°,which means that the optical axis is at 45° to both polarizers. Thelight intensity measured in this position is defined as the bright stateintensity. The contrast of the birefringent LCP-layer is then determinedby the ratio of intensities of bright state to dark state. The contrastratio measured in this way is a measure for the alignment quality of theLCP-layer. If the liquid crystal layer is not oriented at all, then darkand bright state intensities are identical and the contrast ratio is1:1.

Evaluation of Orientation Thresholds

For an efficient manufacturing process it is of interest: a) how muchexposure energy does a photo-alignment layer require to achieve acertain contrast ratio in a LCP layer aligned by the orientation layer.Accordingly, a parameter Ecr500 is introduced, which is defined as thelowest exposure energy for the polymer, for which the contrast ratio inthe LCP layer is 500:1. For the evaluation of Ecr500 the contrast ratiois determined in each of the stripes, which are photo-aligned withdifferent energies, and then Ecr500 is evaluated by interpolation of thecontrast ratio data. b) On the other hand, if the tact times and thepolarized uv-light intensity in a production line are already fixed, theexposure energy for the polymer is also fixed. In that case the questionarises what kind of contrast can be achieved in an LCP layer oriented byan orientation layer exposed to said exposure energy. Therefore, asecond parameter CR4 is introduced for the evaluation in the examples,which is defined as the contrast ratio achieved in a LCP-layer, which isaligned by the orientation layer, wherein the orientation layer has beenexposed to linearly polarized uv-light of 4 mJ/cm².

EXAMPLE 1

For each polymer material listed below, solution S1 was used to prepareLCP-layers, which are aligned by the orientation layer, according to theprocedure described above, which means: preparation of a solution of thepolymer material, preparation of an orientation layer, preparation ofLCP solution S1 and finally the preparation of the LCP-layer, which isaligned by the orientation layer.

The evaluation of the orientation performance parameters is thenperformed as described above.

Ecr500 [mJ/cm²] CR4 poly [1-[3-[4-[(E)-2-methoxycarbonyl-vinyl]- 4.5470:1 phenoxy]-propoxycarbonyl]-1-methyl-ethylene] poly[1-[4-[4-[(E)-2-methoxycarbonyl-vinyl]- 1.8 850:1phenoxy]-butoxycarbonyl]-1-methyl-ethylene] poly[1-[5-[4-[(E)-2-methoxycarbonyl-vinyl]- 2.1 824:1phenoxy]-pentoxycarbonyl]-1-methyl-ethylene] poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]- 1.9 1000:1 phenoxy]-hexoxycarbonyl]-1-methyl-ethylene] poly[1-[7-[4-[(E)-2-methoxycarbonyl-vinyl]- 465:1phenoxy]-heptoxycarbonyl]-1-methyl-ethylene] poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]- 1.8 400:1phenoxy]-octoxycarbonyl]-1-methyl-ethylene]

Ecr500 [mJ/cm²] CR4 poly [1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]- 3 626:1phenyl carbonyloxy]-hexoxycarbonyl]- 1-methyl-ethylene] poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]- 1.8 910:1 phenylcarbonyloxy]-octoxycarbonyl]-1-methyl- ethylene]

Ecr500 [mJ/cm²] CR4 poly [1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-2- 5.6402:1 methoxyphenoxy]-hexoxycarbonyl]-1-methyl- ethylene]; poly[1-[8-[4-[(E)-2-methoxycarbonyl-vinyl]-2- 4.3 474:1methoxyphenoxy]-octoxycarbonyl]-1-methyl- ethylene]

EXAMPLE 2

For each polymer material listed below, solution S2 was used to preparealigned LCP-layers, which are aligned by the orientation layer,according to the procedure described above, which means: preparation ofsolution of polymer material, preparation of a photo-alignment layer,preparation of LCP solution S2 and finally the preparation of thealigned LCP layer, which is aligned by the orientation layer.

The evaluation of the orientation performance parameters was thenperformed as described above.

Ecr500 [mJ/cm²] CR4 poly [1-[10-[4-[2-methoxy-4-[(E)-2- 8  60:1methoxycarbonyl-vinyl]-phenoxycarbonyl]-phenoxy]-decyloxycarbonyl]-1-methyl- ethylene] poly[1-[11-[4-[2-methoxy-4-[(E)-2- 4 500:1methoxycarbonyl-vinyl]-phenoxycarbonyl]-phenoxy]-undecyloxycarbonyl]-1-methyl- ethylene]

What is claimed is:
 1. Polymer material which comprises repeating unitsof formula (I):

wherein M¹ is a monomer unit selected from the group consisting ofacrylate, methacrylate, ring A is unsubstituted phenylene or phenylenewhich is substituted with alkyl or alkoxy, ring B is phenylene, Y¹, Y²are —CO—O—; m, n are both 0; ring C is unsubstituted phenylene orphenylene which is substituted with methoxy, ethoxy, propoxy or butoxy;S¹ is a spacer unit S²; wherein S² is —(CH₂)_(r)—O—, wherein r is 6; Zis —O—, D is methyl, ethyl, propyl; wherein the polymer material is ahomopolymer.
 2. Process for the preparation of polymer material whichcomprises repeating units of formula (I) according to claim 1 comprisingpolymerising a monomer compound of formula (I′)

wherein M² is acrylate, methacrylate; and S¹, A, B, C, D, Y¹, Y², n, mand z have the meanings as described in claim
 1. 3. Monomer compound offormula (I′):

wherein M² is acrylate, methacrylate; and S¹, A, B, C, D, Y¹, Y², n, mand z have the meanings as described in claim
 1. 4. A polymer materialaccording to claim 1 which is poly[1-[6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-hexoxycarbonyl]-1-methyl-ethylene].5. A monomer compound of formula (I′) according to claim 3 which isrepresented by 6-[4-[(E)-2-methoxycarbonyl-vinyl]-phenoxy]-hexyl2-methyl-acrylate.
 6. Composition comprising a polymer material offormula (I) according to claim 1 and optionally a solvent selected fromthe group consisting of γ-butyrolactone, N,N-dimethylacetamide,N-methylpyrrolidone, N,N-dimethylformamide, methylethylketone (MEK),1-methoxypropylacetate (MPA), 1-methoxypropanol (MP).
 7. Method of usingthe polymer material comprising repeating units of formula (I) accordingto claim 1, or a composition thereof, comprising providing the polymermaterial or the composition as orienting layer for liquid crystals. 8.Method for the preparation of an orientation layer for liquid crystalscomprising irradiating polymer material which comprises repeating unitsof formula (I) according to claim
 1. 9. Orientation layers comprising apolymer material which comprises repeating units of formula (I)according to claim 1, comprising said polymer material.
 10. Optical orelectro-optical elements comprising the polymer material according toclaim 1.